Ribose diester quaternary useful as a fabric conditioner

ABSTRACT

Biodegradable compounds which are effective fabric conditioning molecules are described as having Formula I ##STR1## wherein R 1  is a C 1-4  alkyl or alkenyl, R 2  and R 3  are each independently a C 7  -C 30  straight or branched alkyl or alkenyl, R 4  is a C 1-4  alkyl or alkenyl or hydroxyalkyl and X is a water soluble anion.

FIELD OF THE INVENTION

This application is a continuation-in-part of U.S. Ser. No. 08/252,033filed on Jun. 1, 1994, now U.S. Pat. No. 5,429,756. This inventionrelates to novel ribose diester quaternary ammonium compounds which areeffective fabric conditioners and are aquatically non-toxic.

BACKGROUND OF THE INVENTION

Quaternary ammonium salts such asN,N-di(tallowoyl-oxy-propyl)-N-N-dimethyl ammonium methyl sulfate areknown as effective fabric conditioning agents which are also readilybiodegradable as described in U.S. Pat. Nos. 4,137,180; 4,767,547 and4,789,491. The biodegradable cationic diester compounds described inU.S. Pat. No. 4,137,180 are preferred fabric conditioning molecules.

However, it has been observed that some of these fabric conditioningmolecules degrade by hydrolization of one of the ester moieties from themolecule which may result in a monoester which may cause aquatictoxicity.

Therefore, there is a need for novel molecules which are both effectivefabric conditioners and which biodegrade into environmentally friendlyforms.

SUMMARY OF THE INVENTION

It is thus an object of the invention to provide novel compounds whichare both effective fabric conditioners and which hydrolyze to formnon-toxic moieties.

Another object is to provide novel ribose diester quaternary ammoniumcompounds which are effective fabric conditioners useful for fabricsoftening and static control in a variety of stable physical forms.

A further object of the invention is to provide environmentally friendlyfabric conditioning compositions which are also effective fabricconditioners.

Another object is to provide a process for laundering fabrics whichyield good fabric conditioning using the novel biodegradable moleculesof the invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention relates to novel aquatically non-toxic cationicfabric conditioning agents having a Formula I ##STR2## wherein R₁ is aC₁₋₄ alkyl or alkenyl, R₂ and R₃ are each independently a C₇ -C₃₀straight or branched alkyl or alkenyl, R₄ is a C₁₋₄ alkyl, alkenyl orhydroxyalkyl and X⁻ is a water soluble anion.

Preferably, R₁ and R₄ are each a C₁₋₄ alkyl and R₂ and R₃ are each aC₁₅₋₂₈ straight or branched chain alkyl.

The term "water soluble" means that the cationic compounds of Formula Iremain dispersed throughout the laundry solution during the washingprocess.

The anion X⁻ in the molecule is preferably the anion of a strong acidand can be, for example, chloride, bromide, iodide, sulfate and methylsulfate; the anion may carry a double charge in which case X⁻ representshalf a group.

Preferred compounds of Formula I includeβ-methyl-2,3-dipalmitoyl-5-deoxy-trimethylammonium-D-ribofuranosidemethyl sulfate.

Preparation

A concentrated acid was added to a solution of D-ribose in short chainalcohol at 0° C. to 20° C. and stirred for four to six days. Theresulting solution was neutralized and the solvent was removed. Theresidue was then added to a solution of p-toluene sulfonyl chloride inanhydrous pyridine. The resulting compound was mixed withtetrahydrofuran and a dialkyl amine, at a temperature of from about 40°C. to about 60° C. for about one to three days. The resulting productwas added to a solution of a long chain fatty acid in a suitable solventand anhydrous pyridine. The products are isolated as waxy materials. Thedesired product was obtained by quaternization with alkyl chloride (C₁-C₄) or alkyl methyl sulfate (C₂ -C₄). Suitable solvents includemethylene chloride, toluene, and xylene. Long chain amines which can beused are dihexadecyl amine up to 30 carbons and mixtures of differentchains. Long chain esters of amines are also possible by reactingdiethanolamine with nicotinic and then reacting with long chain fattyacids.

The fabric conditioning compositions comprise an effective amount ofFormula I, preferably from about 5 to about 99 wt. %, more preferablyfrom about 10 to about 95 wt. %, most preferably from about 15 to about90 wt. %.

The fabric conditioning compositions may be formulated in a variety ofphysical forms such as liquid, paste, tumble dryer sheets, flakes orgranules. The compositions may also be combined with detergentformulations to provide a laundry detergent which also conditionsfabrics.

Additional Fabric Conditioning Agents

The novel compounds of the invention may also be combined withhydrocarbon fabric agents known in the art to form an active mixture.Preferably, the hydrocarbon softeners are biodegradable.

Examples of such agents include cationic quaternary ammonium salts,tertiary fatty amines, carboxylic acids, esters of polyhydric alcohols,fatty alcohols, ethoxylated fatty alcohols, ethoxylated fatty amines,ethoxylated monoglycerides and ethoxylated diglycerides, mineral oilsand polyols such as polyethyleneglycol, and silicone oils as describedin U.S. Pat. No. 5,254,269 (Taylor et al.).

Optional Ingredients

Other optional ingredients which may be included in the fabricconditioning compositions of the invention include optical brightenersor fluorescent agents, perfumes, colorants, germicides and bactericides,each optional additive being present in an amount of up to about 10 wt.%.

Detergent Formulations

The conditioning compositions of the present invention can beincorporated into both granular and liquid detergent formulations withlittle detrimental effect on cleaning.

The compositions are typically used at levels up to about 30% of thedetergent composition, preferably from about 5 to 20% of thecomposition.

Detergent Surfactant

Detergent surfactants included in the detergent formulations of theinvention may vary from 1% to about 99% by weight of the compositiondepending on the particular surfactant(s) used and the cleaning effectsdesired.

Preferably, the surfactant is present in an amount of from about 10 to60% by weight of the composition. Combinations of anionic, preferablyalkyl sulfates, alkyl ethoxylated sulfates, linear alkyl benzenesulfonates, and nonionic, preferably alkyl polyethoxylated alcoholsurfactants are preferred for optimum cleaning, softening and antistaticperformance. It may be appreciated that other classes of surfactantssuch as ampholytic, zwitterionic or cationic surfactants may also beused as known in the art. As generally known, granular detergentsincorporate the salt forms of the surfactants while liquid detergentsincorporate the acid form where stable. Examples of surfactants withinthe scope of the invention are described in U.S. Pat. No. 4,913,828issued to Caswell et al., herein incorporated by reference.

Builders, accumulating agents and soil release agents known in the artmay also be used in the detergent formulations. Examples of suchsuitable components are described in Caswell et al., U.S. Pat. No.4,913,828, herein incorporated by reference.

Other Optional Detergent Ingredients

Optional ingredients for the detergent compositions of the presentinvention other than those discussed above include hydroropes,solubilizing agents, suds suppressers, soil suspending agents, corrosioninhibitors, dyes, fillers, optical brighteners, germicides, pH adjustingagents, enzyme stabilizing agents, bleaches, bleach activators, perfumesand the like.

EXAMPLES Example 1

β-methyl-2,3-dipalmitoyl-5-deoxy-trimethylammonium-D-ribofuranosidemethyl sulfate is prepared as follows.

To a solution of D-Ribose (80 g, 0.5 mol) in anhydrous methanol (800 ml)in a 2 liter three-neck jacketed round-bottom flask was addedconcentrated sulfuric acid (8-10 ml) at 0°-5° C. and stirred thereaction mixture for four days. Then the solution was neutralized withbasic ion exchange resin. The resin was filtered off and the solvent wasremoved on a rotary evaporator which gave the β-methyl-D-ribofuranosideproduct. The pure β-isomer was obtained by crystallization from ethylacetate, m.p. 79°-80° C. The compound showed the followingcharacteristics: ¹ H NMR (200 MHz, D₂ O) δ 3.40 (s, 3H, OCH), 3.62 (dd,1H, H-5), 3.83 (dd, 1H, H-5), 4.05 (m, 3H, H-2, H-4, OH), 4.14 9s, 1H,OH), 4.17 (dd, 1 H, H-3), 4.91 (s, 1 H, H-1 ).

To a solution of β-methyl-D-ribofuranoside (10 g, 0.304 mol) ionanhydrous pyridine (10 ml) in a 100 ml three-neck round-bottom flaskfitted with a condenser and nitrogen inlet adapter a solution of tosylchloride (12.58 g, 0.066 mol) in anhydrous pyridine (50 ml) was addeddropwise at 0° C. under nitrogen atmosphere. The reaction mixture wasstirred at 0° C. for 3 hours and then at room temperature for threedays. The excess pyridine was removed under reduced pressure which gavethe crude product (15 g, 70% yield). The compoundβ-methy-5-O-toluenesulfonyl-D-ribofuranoside showed the followingcharacteristics: ¹ H NMR (200 MHz, d₆ -acetone) δ 2.45 (s, 3H, CH₃),3.28 (s, 3H, OCH₃), 2.87 (d, 1 H, H-5), 4.02 (m, 4H, H-5, H-2, H-4, OH),4.23 (m, 2H, H-3, OH), 4.71 (s, 1H, H-1), 7.51, 7.86 (ABq, 4H, C₆ H₄).

β-methyl-5-O-toluenesulfonyl-D-ribofuranoside (13.43 g, 0.042 mol) wasadded to anhydrous tetrahydrofuran (40 ml) in a pressure reactor).Dimethylamine was condensed (8 ml) using a dry ice condenser and addedquickly to the reactor. Immediately the pressure reactor was closed andplaced in an oil bath at 50° C. for two days. The excess dimethylaminewas removed by passing nitrogen through the reactor and then thetetrahydrofuran was removed on a rotary evaporator which gave the crudeproduct (6.8 g, 85% yield). 5-N,N-dimethylamino-β-D-methylribofuranosideshowed the following characteristics: ¹ H NMR (200 MHz, CD₃ OD) δ 2.87(s, 6H, CH₃), 3.45 (s, 3H, OCH₃), 3.89 (d, 2H, H-5), 4.02 (dd, 2H, H-2,H-4), 4.19 (m, 2H, H-3, OH), 4.79 (s) 1H, H-1), MS (Cl, isobutane), MH⁺,192.

To a solution of β-methyl-5-deoxy-N,N-dimethylamino-D-ribofuranoside(1.32 g, 0.007 mol) in anhydrous methylene chloride (50 ml) in a 500 mlthree-neck round-bottom flask was added a solution of palmitoyl chloride(2.89 g, 0.011 mol)in methylene chloride (10 ml) and anhydrous pyridine(1 ml). The reaction mixture was stirred at 0° C. for 3 hours and thenat room temperature overnight. Then the reaction mixture was extractedwith methylene chloride (3×100 ml), washed with brine (3×20 ml) anddried over anhydrous sodium sulfate. After filtration the solvent wasremoved on a rotary evaporator which gave the crude product (4.2 g, 90%yield). The crude product was purified on a silica gel column elutingfirst with hexane: ethyl acetate (1:1) and then with chloroform:methanol(9:1). The solvent was removed on a rotary evaporator which gave theβ-methyl-2,3-dipalmitoyl-5-deoxy-N,N-dimethylamino-D-ribofuranoside. Thecompound showed the following characteristics: ¹ H NMR (200 MHz, CDCl₃)δ 0.88 (t, 6H, CH₃), 1.26 (br, 48H, CH₂), 1.62 (t, 4H, CH₂), 2.32 (t,4H, CH₂), 2.94, 3.01 (2s, 6H, CH₃), 3.36 (s, 3H, OCH), 4.09 (m, 3H, H-2,H-3, H-4), 4.82 (s, 1H, H-1), 5.16 (m, 2H, H-5), ¹³ C NMR (50 MHz,CDCl₃) δ 14.14, 22.65, 22.73, 22.80, 24.81, 24.97, 25.23, 28.73, 29.09,29.16, 29.27, 29.35, 29.41, 29.55, 29.73, 29.82, 29.88, 31.89, 31.96,32.02, 33.45, 34.02, 34.07, 35.35, 45.59, 45.66, 45.73, 55.19, 63.42,73.46, 78.90, 106.46, 172.46, 172.58, MS (Cl, isobutane), MH⁺ 668.

To a solution ofβ-methyl-2,3-dipalmitoyl-5-deoxy-N,N-dimethylamino-D-ribofuranoside(0.647 g, 0.001 mol) in anhydrous toluene (5 ml) in a 100 ml two-neckround-bottom flask was added dimethylsulfate dropwise at roomtemperature. The reaction mixture was stirred at room temperatureovernight. The solid was removed by filtration and then recrystallizedfrom diethylether which gaveβ-methyl-2,3-dipalmitoyl-5-deoxy-trimethylammonium-D-ribofuranoside(0.75 g, 95% yield) m.p. 79°-81° C. The compound showed the followingcharacteristics: ¹ H NMR (200 MHz, CDCl₃) δ 0.85 (t, 6H, CH₃), 1.26 (br,48H, CH₂), 1.59 (m, 4H, CH₂), 2.33 (m, 4H, CH₂), 3.40 (s, 9H, CH₃), 3.43(s, OCH₃), 4.91 (s, 1H, H-1), 5.18-5.26 (m, 2H, H-2, H-3), 13C NMR (50MHz, CDCl₃) δ 14.13, 22.71, 29.38, 29.73, 33.91,54.33, 56.21, 69.58,72.51, 72.88, 74.72, 107.46, 172.32, 162,91, MS (FAB), C⁺, 668.

Example 2

A fabric conditioning composition containing the ribose diesterquaternary compound of Example 1 was prepared. A 5% dispersion of theribose diester quaternary was prepared by adding the active todemineralized water and heating the mixture to 75° C. to form ahomogeneous dispersion (Sample A).

A 5% dispersion of N,N-di(tallowoyl-oxy-propyl)-N,N-dimethyl ammoniummethyl sulfate was also prepared under the same procedure (Sample B).

Example 3

To evaluate the softening performance of the novel compound, two gramsof each of Samples A and B were separately added to a liter of tap waterat ambient temperature containing 0.001% by weight of sodium alkylbenzene sulfonate to simulate carryover of anionic detergent active fromthe wash. 800 ml of the obtained solution of each sample were put in aTergotometer pot and four pieces of terry towel (40 grams total weight)were added. The cloths were treated for five minutes at 60 rpm, spundried and line dried. The dried fabrics were assessed for softness by anexpert panel using a round-robin test protocol which assigned a numberfor softness performance.

Softness performance by softness scale was as follows:

                  TABLE 1                                                         ______________________________________                                                Sample A                                                                              2.5                                                                   Sample B                                                                              3.5                                                           ______________________________________                                    

The softening performance of the ribose diester quaternary compound wascomparable to that of the prior art compound of Sample B. Thus, theribose diester quat shows a good softening effect on fabric.

Example 4

The biodegradability of the compound of Example 1 was evaluated by amodified Sturm test and found to exhibit 59% degradation.

The Modified Sturn Test Procedure

The Modified Sturm Test was adopted by the OECD on May 12, 1981 andrenamed as the 301 B CO₂ Evolution Test in early 1993, hereinincorporated by reference.

A high biodegradation result in this test provides the evidence that thetest compound is highly biodegradable in aerobic systems.

The test is started by bubbling CO₂ -free air through the solution at arate of 50-100 ml/min per carboy (approximately 1-2 bubbles/second). TheCO₂ produced in each carboy reacts with the barium hydroxide and isprecipitated out as barium carbonate; the amount of CO₂ produced isdetermined by titrating the remaining Ba(OH)₂ with 0.05N standardizedHCl (see below). Periodically (every 2 or 3 days), the CO₂ absorbernearest the carboy is removed for titration. The remaining two absorbersare each moved one place closer to the carboy, and a new absorber filledwith 100 ml of fresh 0.025N Ba(OH)₂ is placed at the far end of theseries. Titrations are made as needed (before any BaCO₃ precipitate isevident in the second trap), approximately every other day for the first10 days, and the every fifth day until the 28th day.

For water-insoluble test materials, incorporated dry into the CO₂ testcarboy, agitation can be done with a magnetic stirrer. For foamingchemicals, CO₂ test carboy, agitation can be done with a magneticstirrer. For foaming chemicals, CO₂ -free air bubbling can be replacedby overhead aeration and magnetic stirring.

On the 26th day, the pH of the carboy contents is measured again, andthen 1 ml of concentrated HCl is added to each of the test carboys todrive off inorganic carbonate. The carboys are aerated overnight, andsamples are removed from each carboy for dissolved organic carbon (DOC)analysis. The final titration is made on day 28.

Titrations of the 100-ml Ba(OH)₂ solution are made after removing thebottles closest to the carboys. The Ba(OH)₂ is titrated with 0.05N HCl,using phenophthalein as an indicator.

The test is run at room temperature and temperature is recorded duringthe test period.

Theoretical amount of CO₂ is compared to amount of CO₂ produced todetermine the biodegradation of a test material.

We claim:
 1. A compound having a Formula I ##STR3## wherein R₁ is a C₁₋₄alkyl or alkenyl, R₂ and R₃ are each independently a C₇ -C₃₀ straight orbranched alkyl or alkenyl, R₄ is a C₁₋₄ alkyl or alkenyl or hydroxyalkyland X⁻ is a water soluble anion.
 2. The compound according to claim 1wherein R₁ and R₄ are each a C₁₋₄ alkyl and R₂ and R₃ are each a C₁₅₋₂₈straight or branched chain alkyl.
 3. The compound according to claim 2wherein R₄ is methyl.
 4. The compound according to claim 1 wherein X isselected from the group consisting of a halide, a sulfate and a nitrate.5. The compound according to claim 4 wherein X is selected from a groupconsisting of a chloride, a bromide, an iodide and a methyl sulfate. 6.The compound according to claim 1 wherein the compound isβ-methyl-2,3-dipalmitoyl-5-deoxy-trimethyl ammonium-D-ribofuranosidemethyl sulfate.
 7. A fabric conditioning composition comprising:about 1to about 99 wt. % of a compound having a Formula I ##STR4## wherein R₁is a C₁₋₄ alkyl or alkenyl, R₂ and R₃ are each independently a C₇ -C₃₀straight or branched alkyl or elkenyl, R₄ is a C₁₋₄ alkyl or alkenyl orhydroxyalkyl and X is a water soluble anion; and about 99 wt. % to about1 wt. % water.
 8. The composition according to claim 7 wherein thecomposition comprises from about 15 to about 90 wt. % of the compoundsof Formula I.
 9. The composition according to claim 7 further comprisinga hydrocarbon fabric conditioner active.
 10. The composition accordingto claim 7 wherein the composition further comprises at least oneadditive selected from the group consisting of an optical brightener, afluorescent agent, a perfume, a colorant, a germicide, a bactericide andmixtures thereof, the amount of each additive being up to about 10 wt.%.
 11. The composition according to claim 7 wherein the compound ofFormula I is β-methyl-2,3-dipalmitoyl-5-deoxy-trimethylammonium-D-ribofuranoside methyl sulfate.